JPH0423894A - Lubricating oil composition for engine - Google Patents

Abstract

PURPOSE:To obtain the subject economical composition having excellent heat- resistance by using a specific saturated alcohol, ether or ketone compound and a specific metal-type detergent as essential components at specific ratios. CONSTITUTION:The objective composition contains, as essential components, (A) 0.01-5.0wt.% of one or more compounds selected from (i) 6-22C (preferably 6-20C) saturated alcohol, (ii) 6-14C (preferably 6-12C) ether and (iii) 6-18C (preferably 6-16C) ketone compound and (B) 1-50wt.% of a metal-type detergent such as a mixture of alkaline-earth metal chlorosulfide of a hydroxyalkylbenzoic acid and an alkylphenol, an alkaline-earth metal salicylate, an alkaline-earth metal phenate and an alkaline-earth metal sulfonate.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to lubricating oil compositions for engines.

j? Hc, a saturated alcohol, ether or ketone (hereinafter referred to as an oxygen-containing compound) with a specific carbon number and a metal type that maximizes its ability in fields where engine oil is required to have a long life under high-temperature engine conditions. The present invention relates to an engine lubricating oil composition having excellent heat resistance and containing a detergent as an essential component.

[Conventional technology]

The demand for higher output from automobile engines is becoming more severe year by year, and improving the fuel efficiency of automobiles is an important issue, so efforts are being made to improve the thermal efficiency of engines. It tends to become. In marine engines as well, regardless of whether they are trunk piston engines or crosshead engines, the temperature inside the engine tends to rise year by year due to the trend toward higher output and fuel efficiency. Furthermore, in recent years, due to heightened awareness of energy conservation, total energy systems with high energy efficiency have become rapidly popular.

Since the total energy system recovers exhaust heat from the engine, the temperature of the cooling water is set high, resulting in high temperatures inside the engine.

It is desirable for engine oils used under high-temperature conditions to have improved heat resistance, but in order to improve the heat resistance of engine oils, metal detergents, which are the main additives for engine oils, have traditionally been effective in improving heat resistance. For this reason, 7enate or salicylate is used.

The present inventors have previously attempted to improve heat resistance by combining a sulfurized mixture of alkaline earth metal salts of hydroxyalkylbenzoic acid and alkylphenol with polyol ester (4!) (Kokai 1-204994); Heat resistance was further improved by combining 6 to 22 fatty acids and a metal type detergent (%
-227777').

[Problem to be solved by the invention]

However, it would be preferable if cheaper and more effective additives could be found in addition to the combination of the above additives, since this would broaden the range of selection.

The problem to be solved by the present invention is that the inventors focused on the fact that the combination of a specific fatty acid provided in a previous application and a metal-type detergent has a synergistic effect on heat resistance. The aim is to find a third substance that exhibits a synergistic effect on the

[Means and effects for solving the problems] As a result of intensive studies to solve the above problems, the present inventors have found that a lubricating oil composition consisting of a specific oxygen-containing compound and a metal-type detergent solves the above problems. The inventors have discovered that the present invention has been completed.

That is, in the present invention, a saturated alcohol having 6 to 22 carbon atoms, an ether having 6 to 14 carbon atoms, or a ketone compound having 6 to 18 carbon atoms is added in an amount of 0.01 to 5.01 s or more to a pot and a metal type detergent of 1 to 1 s. A lubricating oil composition for an engine, characterized in that it contains 50% by weight as an essential component.

The oxygen-containing compound, which is one of the components of the composition of the present invention, is a saturated alcohol having 6 to 22 carbon atoms, an ether having 6 to 14 carbon atoms, or a ketone compound having 6 to 180 carbon atoms.

Saturated alcohols having 6 to 22 carbon atoms, preferably 6 to 20 carbon atoms, include n-hexyl alcohol, 2-ethyl-1
-butanol, n-hexyl alcohol, 2-heptatool, n-octyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, lauryl alcohol,
Examples include 1-tridecyl alcohol, 2-tridecyl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, stearyl alcohol, 1-eicosanol, and 1-docosanol.

The number of ethers per gram of charcoal is 6 to 14, preferably 6 to 12,
For example, n-propyl ether, isopropyl ether,
Examples include n-butyl ether, syn-n7-myl ether, in-amyl ether, and the like.

Ketone compounds having 6 to 18 carbon atoms, preferably 6 to 16 carbon atoms, include methyl-roptyl ketone, methyl-iso-butyl ketone, di-imbutyl ketone, in-amyl methyl ketone,
Examples include methyl-0-amyl ketone, di-n-butyl ketone, di-imbutyl ketone, methyl-n-hebutyl ketone, methyl-n-nonyl ketone, and the like.

These oxygen-containing compounds may be linear or branched.
・.

The other metal-type detergent is hydroxyalkyl-based x
Sulfurized mixtures of alkaline earth metal salts of monoxide and alkylphenols, alkaline earth metal salicylates, alkaline earth metal phenates, alkaline earth metal sulfonates, and the like are used.

Alkaline earth metal salt sulfurized mixtures of hydroxyalkylbenzoic acids and alkylphenols (hereinafter referred to as sulfurized mixtures).

It is called "Hydroxybenzoate/Septate Sulfide Mixture". ), a reaction raw material mixture consisting of phenols, dihydric alcohols, and alkaline earth metal oxides or hydroxides having a Durham equivalent ratio to phenols of 0.99 or less, or mixtures thereof, is reacted, and then water and metal The dihydric alcohol is distilled off until it becomes 0.6 mol or less per 1 mol of reagent, and the resulting distillation column bottom is reacted with a carbon dioxide longitudinal cable.
It is obtained by reacting 4.0 moles of elemental sulfur and is detailed in JP-A-64-29354.

Typical examples of alkaline earth metal salicylates include calcium salts, magnesium salts, etc. Generally, phenol is alkylated with an α-olefin having 14 to 18 carbon atoms to form an alkali metal salt, and the carboxyl group is converted into an alkali metal salt by Kolbe-Schmidt reaction. 24560 of the 1980s and 24560 of the 1980s;
I am familiar with 24561 etc.

The alkaline earth metal phenate is an alkaline earth metal salt of an alkylphenol compound to which an alkyl group having an alkyl group of about 8 to 30 has been added, and is preferably a calcium, magnesium or barium salt.
393, the product is Cosmo PAD210 (Cosmo Oil Co., Ltd.).

Alkaline earth metal sulfonate has a molecule position of 400 to 60
0 lubricating oil or an alkaline earth metal salt of a sulfonated synthetically alkyl-substituted aromatic compound,
Calcium, magnesium or barium salts are preferred. These metal-type detergents may be neutral or overbased with a base number of 300 or higher and comply with USP 30.
57896, USP 4129589, etc.

The overbased type is also produced by treating the neutral type with carbon dioxide.

A preferred embodiment of the present invention has a viscosity of about 4 to 1000
A saturated alcohol having 6 to 22 carbon atoms, an ether having 6 to 14 carbon atoms, or a saturated alcohol having 6 to 22 carbon atoms, an ether having 6 to 14 carbon atoms or One or more of the ketone compounds of numbers 6 to 18 in a proportion of about 0.01 to 5, preferably about 0.05 to 3, and a metal-type detergent in a proportion of about 1 to 50, preferably about 3 to 30. A lubricating oil composition for an engine is prepared by blending the following proportions.

In the engine lubricating oil composition according to the present invention, if the amount of both the oxygen-containing compound and the metal type detergent is too small, the composition will have poor heat resistance, and if the amount is too large, the cost will increase, which is disadvantageous. The engine lubricating oil composition of the present invention can be used as a gasoline engine oil, diesel engine oil, marine engine oil, etc. The engine lubricating oil composition of the present invention contains an oxygen-containing compound and a metal-type detergent as essential components. , the lubricant base oil may or may not be mixed, and further includes ashless dispersants, anti-wear agents, antioxidants, corrosion inhibitors, viscosity index improvers, which are commonly added to engine oils.
It may also contain a pour point depressant, an antifoaming agent, and the like.

As the ashless type dispersant, succinimide, succinate ester, benzylamine, etc. to which an alkyl group or alkenyl group having a molecular weight of about 700 to 3000 is added are used. Furthermore, borated succinimide can also be used. These ashless type dispersants are generally incorporated in the composition in an amount of 0.5 to 15% by weight.

Examples of anti-wear agents include zinc dialkyldithiophosphate. Examples of the antioxidant include amine type antioxidants and phenolic type antioxidants. Examples of corrosion inhibitors include benzotriazole and alkenyl succinic esters.

These generally occupy 6.1 to 3 parts by weight in the composition.

Examples of viscosity index improvers include polymethacrylates and olefin copolymers. Examples of pour point depressants include polymethacrylate. Examples of antifoaming agents include silicon compounds. The blending amount of these additives is 20% by weight or less, preferably 10% by weight or less.
% by weight or less.

The present invention is a lubricating oil composition suitable for high-temperature engines.

Normally, under the operating conditions of an engine, the cylinder wall temperature rises to a maximum of 220-230 t:', but the composition of the present invention allows the temperature to rise even higher, e.g.
It can withstand operating temperatures of 270C.

〔Effect of the invention〕

Although the composition of the present invention only contains as essential components an inexpensive oxygen-containing compound such as a saturated alcohol, ether, or ketone compound of a specific number, and a metal type detergent,
This product has the advantage of exhibiting better heat resistance than conventional products.

〔Example〕

The present invention will be explained below with reference to Examples, Comparative Examples, and Reference Examples. The following reference example shows a production example of a sulfurized hydroxybenzoate/phenate mixture to be added to the composition of the present invention.

Reference Example 1 Nonylphenol 237954 was placed in a 5J autoclave equipped with a stirrer, cooling tube, nitrogen gas introduction tube, and thermometer.
(10.8 mol), 98.4% pure calcium oxide 2
05f (3.6 mol) was added and stirred. This suspension contains ethylene glycol 345) containing 2.8 wt% of water.
(5.4 mol) under a pressure of 6 kpZ in a nitrogen stream, 1
After reacting at 160C for 3 hours, while gradually reducing the pressure of the reaction system, added water, produced water,
By distilling off most of the added ethylene glycol and some of the nonylphenol, a dark, dark liquid distillation residue 2358P was obtained. In this case, the temperature of the bottom product at the end is 180C1, and the temperature of the distillate is 160C (11
It was WHri).

Next, 12Or, 22w,
275 d/min (6ky10x
Carbon dioxide was blown in at the flow rate of 2) for about 0.6 hours to a pressure of 5.3 ky/en2. After that, the temperature was raised to 178C, and then carbon dioxide was blown in again to 6 ky/c.
The pressure was increased to 2508 P and kept at that state for 4 hours to obtain a dark gray-yellow-red liquid reaction product 2508P. The calcium content of this reaction product was 5.76 wt%.

In addition, 2.0OF of this reaction product was taken into a separating funnel,
601 in ether, IN sulfuric acid 151L7!
was added and stirred for 6 o'clock on a shaker for hydrolysis), and after thorough washing with water, the ether layer was separated and the ether was removed using a rotary evaporator to obtain a brown liquid (1.88). The acid value of this liquid is s+w9KOH
/7.

Next, the carbon dioxide treatment product 4 in the autoclave is
18y-1! Transfer to an autoclave and add sulfur z3. xy
(o, 72 mol) was added at 149 C under normal pressure in a stream of CO2, and then the temperature was increased to 178 cK at 6 C at positive pressure CO1.
ky 15 FI" and stirred at the above temperature for 4 hours to obtain a very dark yellow-red liquid product of 436.4 F. The acid number of this product (determined as above).

same as below. ) was 53 ■K OH/P.

392.3 of the above sulfurization reaction product was placed in a 1L three-necked pear-shaped flask.
5' and 150 =, -toral oil (100C'f, paraffinic lubricating oil with a viscosity of 5J8cSt) Obtained 330.9P. The final distillate temperature at that time was 190c (2wHP). Then, the extremely small amount of undissolved soybean contained in this distillation residue was removed by filtration, resulting in a viscosity of 131.3 cSt (@ 10
A final product 328.72 was obtained as a very dark yellow-red transparent viscous liquid having a base value of 74N9KOH/), a calcium content of 6.20 wt%, and a sulfur content of 3.32 vvt%.

Reference Example 2 Recovered nonylphenol (nonylphenol 89.8%, ethylene glycol 1.4 g,
Mineral oil 8.8%) 386.4), fresh nonylphenol 115.7), calcium oxide 97.4% pure 40.
354 (C)-7 mol) was added and stirred. In this suspension, water a, ethylene glycol 61 containing 1Wt4
．． 7 f (0.96 mol) in a nitrogen stream at 4 kP/
Added at 155c under pressure of on2, this was added at 160c
After reacting at C for 3 hours, the added water, produced water, ethylene glycol, and some nonylphenol were distilled off while gradually reducing the pressure of the reaction system, resulting in a dark liquid distillation residue 534? was gotten. At that time, the temperature of the column bottom at the end was 176C', and the distillate temperature was 150r: (
27 H? )Met. Analysis of the distillate revealed that 0.3 mol of ethylene glycol remained in the distillation residue per 1 mol of calcium.

Next, the distillation residue 5341 is s Oxd/rnin (6kt/cpn2) from the state of 132c, 2o HP.
f) Carbon dioxide was bubbled in part at RM for 0.9 hours to a pressure of 5.8 kg/cIR2. After that, the temperature was increased to 17
After reaching 8c, blow in the two-liquefied carbon again to 6kP/c.
The pressure was increased to MI2 and held there for 4 hours, yielding a dark gray-yellow-red liquid reaction product, 566.17. The acid value of this liquid is 33W9KOH/? Met.

Next, the carbon dioxide treatment product 5 in the autoclave is
S1f was sulfur 28.4l-17 in Co2 gas i under normal pressure.
7r, then under CO2 pressure (6ky/cN1”
), stirred at 178c for 4 hours to produce sulfurized reaction product 559
．． I got 35'. The acid value of this product is 23ηK OH/
It was S'.

The above sulfurization reaction product 306.4 was placed in a pear-shaped flask.
Filled with fP and 150 neutral oil 111.6S',
Most of the nonylphenol and a small amount of lubricating oil fraction were distilled off to obtain a distillation residue of 231.5 SF.

The final distillate temperature at that time was 172C (3■H?). Then, a very small amount of undissolved soybean contained in this distillation residue was removed by filtration, and the viscosity was 71.9 cSt (@1
100C), base number 171 MgxOH/P, calcium amount 6.09 wt ql), sulfur amount 3.16 wt ql
A final product 219i was obtained.

Examples 1 to 14, Comparative Examples 1 to 5 Engine lubricating oil compositions as shown in Tables 1, 2, and 3 were prepared.

A hot tube test was conducted to evaluate the heat resistance of engine lubricating oil compositions. This exam is SAE pa
It is said that there is a correlation with the Caterpillar platform engine test that evaluates the high-temperature cleanliness of engine oil, as described in 840262.

The outline of this test is as follows. Air is pumped into the heated glass tube (310t1m) until the sample oil reaches 0.
Injected at 3m/h. The injected sample oil moves up and down in the glass tube and is gradually discharged from the upper outlet. 16
After a period of time, the glass tube is taken out, washed with normal hexane, dried, and evaluated for lacquer adhering to the inner wall of the glass tube. i;! The score was 10 points for colorless and transparent material with no lacquer attached, and 0 point for black and opaque material. The experimental results are shown in Tables 1 to 3.

The metal type detergent used here contains C in the lubricating oil composition.
a amount 0.71 i view%1M5'fi0.47 weight section, B
One amount was 3.9 weight in winter.

Claims (1)

[Claims] (1) Saturated alcohol with 6 to 22 carbon atoms, 6 to 1 carbon atoms
1 of 4 ethers or ketone compounds having 6 to 18 carbon atoms
0.01 to 5.0% by weight of seeds or more and metal type detergent 1 to 5
A lubricating oil composition for an engine, characterized in that it contains 0% by weight as an essential component.